Haloethylene polymers containing allyl ethers of 2-hydroxy benzophenones



'ticularly ultra-violet light. pounds vary in their ability to absorb ultra-violet light' United States Patent HALOETHYLENE POLYMERS CONTAINING AL- r sg. ETHERS or z-rrrnnoxv BENZOPHE- 3 Claims. or. 260-4535) Drawing.

This invention relates to new organic compounds and to polymeric compositions containing the same. More particularly it' relates to new organic compounds finding utility as light stabilizers for haloethylene polymers.

Haloethylene polymers such as those containing at least 50 percent vinylidene chloride, are known to be highly sensitive to the effects of elevated temperatures and of light and under prolonged exposure to heat and light may'become so degraded and discolored as to be commercially useless. It has been common practice to blend certain compounds with the polymer to stabilize it against the degradative elfects of heat and light. Several of such compounds, however, are highly colored materials which impart' an objectionable initial color to the stabilized composition which prevents the production of a commercially saleable white composition. Still other disadvantages of many of theprevious compounds are a high odor level and volatility, Any odor in the stabilizer will be transferred to the stabilized composition. When volatile stabilizers are employed the stabilizers volatilize out of the composition leaving the composition in time unprotected against the degradative effects of light, par- In addition all of the comand it is impossible to predict the effectiveness of any particular compound with any degree of certainty, and even then some of the initially useful compounds wherein the compositions lose some of their effectiveness for absorbing ultra-violet light over a prolonged period of time.

In view of the above problems it would be desirable and it is the principal object of this invention to provide a new group of organic compounds having the stated utility.

It is a further object to provide a group of such compounds which have little or no color and have a low odor level.

Another object is to provide a group of such compounds which have low volatility.

The above and related objects are accomplished by means of a group of allyl ethers of hydroxybenzophenone derivatives having the general formula:

OH g Y wherein X is selected-from the group consisting of hyphenone were dissolved in one literof alcohol. One

mole of allyl chloride was added dropwise and the reaction solution. was heated at reflux for two hours. The reaction solution was then cooled and poured into an excess of water. The mixture was allowed to stand overnite and the product extracted with benzene. The product was distilled at 1 millimeter mercury collecting that portion from 166 to 178 C. The crude product was recrystallized from methanol. The pure 2-hydroxy-4- (2,3-propenoxy) benzophenone was in the form of pale yellow crystals melting at 67.5 to 68.5 C. .Astypical of other representative ethers may be mentioned:

2-hydroxy-3-benzoyl-4-(2,3-propenoxy)benzophenone 2-hydroxy-4"chloro-4(2,3 propenoxy)benzophenone 2-hydroxy-4-ethyl-4-(2,3-propenoxy)benzophenone The ethers of this invention are efiective stabilizers for haloethylene polymers, particularly those polymers containing at least 50 percent vinylidene chloride. Such polymers are known to be especially sensitive to the degradative eifectsof light and are accordingly preferred subjects for such stabilization. The ethers are effective when employed in a concentration of from 0.5 to 6.0

' percent by weight based on the'weight of the polymer used in the formulation. Compositions containing less than 1 percent exhibit little more stability than unstabilized compositions No beneficial result accrues from the use of more than 6 percent, and the cost and physical properties, such as strength, which are dependent largely on the polymer suffer.

The ethers of this invention may, if desired, be blended with the polymer by any knownformulating procedure, such as milling, dry blending, and similar procedures. However, since the ethers of this invention are olefinically unsaturated materials, they may be included as polymen'zable components in the initial polymerization recipe. In that procedure the light stabilizing adjuvant becomes a permanent part of the polymer itself and cannot be leached or removed from the polymer except by chemical reaction to cleave the ether linkage or to neutralize or to destroy the active hydroxybenzophenone structure. Additionally since most commercial-polymerization reactions are conducted in aqueous dispersion with agitation there is good assurance that the light stabilizer will be uniformly distributed throughout the poly-. mer. Uniform distribution of, any additive throughout a polymer formulation using the conventional post-polymerization formulating techniques is a time consuming and costly operation.

The ethers may be used in polymer compositions in conjunction with the other common additives, such as pigments, fillers, heat stabilizers, and plasticizers. They likewise may be employed in combination with other known light stabilizers.

' The advantages of the compositions of this invention will be more apparent from'the' following illustrative example wherein all parts and percentages are by weight.

Example Basic polymer formulations were prepared by blending 89.5 parts of a copolymer prepared from percent vinylidene chloride and 15 percent vinyl chloride with 7 parts of a pentaeryth ritol tetraester whose ester groups had an average of 8 to 10 carbons, and 0.5 part of sodium tripolyphosphate as a heat stabilizer. One'of the basic formulations was left unstabilized to light for use as a blank. To one was added 3 parts of phenyl salicylate for comparative purposes, and to another was added 3 parts of 2-hydroxy-4-(2,3-propenoxy)benzophenone. Moldings having a thickness of 0.1 inch were prepared and exposed to ultraviolet sunlamps for 4 days. The moldings were examined visually following exposure for discoloration and rated according to an arbitrary scale wherein means colorless, 5 means tan, means brown, means dark brown, and means black. It was found that the unstabilized formulation rated 17, the formulation stabilized with phenyl salicylate rated 7, and the formulation stabilized in accordance with this invention rated 2. l 1

Similar results are obtained in stabilizing polyvinyl chloride with the new ethers.

I claim:

1. A light stable thermoplastic composition comprising a haloethylene polymer and from 0.5 to 6 percent of the weight of said polymer of an allyl ether of a 2-hydroxybenzophenone derivative having the general formula:

wherein X is selected from the group consisting of hydrogen, ethyl, and chlorine, and Y is selected from the group consisting of hydrogen and benzoyl. f

2. The composition claimed in claim 1 wherein said allyl ether of Z-hydroxybenzophenone is 2-hydroxy-4- (2,3-propenoxy)benzophenone.

3. The composition claimed in claim 1 wherein said haloethylene polymer is a copolymer composed of at least percentby weight of vinylidene chloride.

References Cited in the file of this patent UNITED STATES PATENTS 2,182,786 Coleman Dec. 12, 1939 2,434,496 Houtman Jan. 13, 1948 2,628,559 Stanley June 29, 1954 2,659,709 Daglish Nov. 17, 1954 2,853,521 Hardy et al 'Sept. 23, 1958 OTHER REFERENCES Fuson et al.: Journal American Chemical Society 73, 49801, October 1951. (Copy in Library.)

UNITED STATES PATENT OFFICE CERTIFICATE OF "GORRECTION Patent No. 2937,15? May 17, .1960

Gerald A. Clark It is hereby certified that error appears in theprinted specification of the above numbered patent requiring correction and that the said Letters Patent should read as corrected below. I

Column 3, line 17,.on the second benzene ring, for s'fX" read Y Signed and sealed this 6th day of December 1960.

(SEAL) Attest:

ROBERT C. WATSON Commissioner of Patents KARL H. AXLINE Attesting Ofiicer 

1. A LIGHT STABLE THERMOPLASTIC COMPOSITION COMPRISING A HALOETHYLENE POLYMER AND FROM 0.5 TO 6 PERCENT OF THE WEIGHT OF SAID POLYMER OF AN ALLYL ETHER OF A 2-HYDROXYBENZOPHENONE DERIVATIVE HAVING THE GENERAL FORMULA: 